Azo dyestuffs and process of making same



Patented May 13, 1930 "UNITED STATES" PATIENT OFFICE WERNER ZERWECK, OF FEGHENHEIM, NEAR ERANKFOBT-ON-THE-MAIN, GERMANY,

ASSIGNOR T GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORA- TION OF DELAWARE AZO' DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Original application filed November 15, 1926, Serial No. 148,620, and in Germany November 17, 1925. Divided and this application filed October 21, 1927. Serial No. 227,858. 1

in which formula the phenylresidue may be further substituted in addition to the aminogroup and R means alkyl or the residue:

5 and a process of making same, said dyestuffs having probably the general formula: no

These derivatives of 2.3-hydroxynaphthoic acid have not been describedhitherto in the literature. They are easily obtainable by condensing, according to U. S. A. Patent 1,101,111, one or two molecular proportions of 2.3-hydroxynaphthoic acid with the corresponding aromatic monoor diamines conin which formula the phenylresidue may be further substituted in addition to the aminogroup and R means alkyl or the residue: I

alryl taining the thiazolic group in their molecule. N The aminothiazolic compounds may be pre- N pared by allowlng acid ClllOllClGS or anhydrides to act on ortho-amino-arylmercaptanes containing an acylamino in the arylresidue, and splitting oii' the acylresidue afterwards, or by allowing nitrosubstituted acid chlorides or anhydrides to act on orthoamino-arylmercaptanes and reducing the nitrogroup afterwards.

The aforesaid methods fol-preparing 2.3- hydroxynaphthoylaminothiazol compounds The new dyestuffs may be obtained by combining any diazocompound not containing a sulto-uic group with a derivative of 2.3-hydroxyi'mphthoic acid of the general formula:

on S may be illustrated by the following scheme C0-NHphenyl N C-R, of equations:

NH /CCH2 1 g/ 6 4 cmcoNnacetic acid CHQCONH\ 5 anhydride saponification 1-mercapt0-2-amino-5-aeety1aminobenzene fi-acetylaminc-2-methyl-benzothiazole s i S \2 2 C CHS CClll 7 I Ny 0 II V 7 N/ n 6 4 3\ condensation with 6 4 3 5 2.3-hydroxynaphthoic acid (i-amIno-l-inethyl-benzothiazole 2.3-11ydrm)-uaphthoyl-lS-amino-Z-methyl-benzothiazole hydroxynaphthoic acid 2-(m-aminophenyl)oamino-benzothiazole The new dyestufl's yield valuable color lakes when mixed with the usual substrate.

They are particularly adapted for being produced on the vegetable fibre, because the derivatives of 2.3-hydroxynaphthoic acid of the above-said formula are distinguished by an especial aiiinity to the vegetable fibre. It is therefore not necessary to dehydrate the padded dyegoods as far as possible by squeezing, pressing or centrifuging prior to devel oping, it being suflicient to treat the padded dyegoods in moist condition with any usual rlnsing solution. The dyeings, Obtained by developing with various diazosolutions,

-'range from yellowish to black and possess remarkable brightness and intensity and, owing to the substantive character of the used azocomponent, an especial fastness to rubbing.

In order to further illustrate my invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, it being understood that my invention is not limited to the particularproducts or reaction conditions mentioned therein.

Example-The cotton yarn is impregnated with a solution containing 10 gm. of the 2.3-hydroxynaphthoyl-compound of '2-methyl-6-amino-benzothiazol, 17 cc. of caustic soda solution of 34' Be. and 25 cc. of Turkey red oil per litre. The goods are then well wrung out, rinsed; and, Without being dried,

' developed with a diazosolution neutralized with a solution of sodium acetate and containing 2 gm. of 1netanitro-0rthoanisidine per iii re.

"lhe dvestuii, thus produced on the fibre, having probably the formula:

OCH.

S-C-C Ha dyes a brilliant bluish red of an excellent fastness,

The aforesaid Q-methyl-G-amino-benzothiazol may, for instance, be prepared by allo\ving disulfur dichloride to act on para-aminoacetanilide (of. British Patent 17417/14), treating the compound thus obtained with an alkali, whereby the ihiazthionium ring is split and the corresponding ortho-aniinoarylniereaptane is obtained, forming then the thiazolic ring by treating it with acetic acid ai'ihydride and finally saponifying the acetyl group. The amino compound thus obtained is easily soluble. in dilute hydrochloric acid and is separated unchanged by adding an alkaline v olution to this arid solution.

lot.

The production of Q-methyl-G-mnino-benzothiazole may be illustrated in the follow ing manner:

disulfur-dichloride doonb thiazthionium compound p-aminoacetanilide Saponification with alkali NH (C [Ia terial accordingto the usual method or also in which formula the phenyl residue in 1ddltion to the anuno group nmy be further substituted and R means alkyl or the residue:

m N i ll N which dyestuffs yield upon reduction with stannons chloride an arylainine and the corresponding derivzitive oi" the l-tlllllIlO-Q-ll)" (.lroxy nu phthaleue- 3 carboxyan'iide, which dyestuffs are adapted for the production of valuable color lakes, when mixed with the usual substrate. undyield when produced on 8 the vegetable fibre dyeings of a renmrkuble brightness and intensity and an excellent l'nstue.-;s especially to rubbing.

2. T he process of nmhing new uzodyestufi's according to the nitrosuniine printing proe whlch C(mlpnses comlmlmg amnmtlc 0% -:1zoco1npound, not cont-tuning a sulfonle In the Same manner the PYOCQSS may be g1() llp,"1tl1tLtlQIlVtllLlVG 0t 2.8-hydroxynaphconducted with other diazo-. tetrazoor p'olythow'acld of the genera-1 formula: nzo bodies and the 2.3-hydroxy-naphthoyl- W compounds of other thla /iohe derivatives.- 0H

The following" table gives the. shades ob- CO NH h 1 s C R tamed on cotton material by producing some p other dyestuffs according to my process: 'lwo molecular proportions of the dinzocmnnnnml or one Combined with the di-?.3-hydroxynaphthoylderivaghams molecule.- proportion of the tetnnzoconmouml of: tives of:

Metu-niLro-para-toluidine Q-(p-znninophenyl)-6-mnino-benzothiazole of the iormula: Brownish red IIQN" 4 5 p-chloroo-tol11i(line Do. Red 1i-1 -ilimninodiphenylnmine D0. Black o-pbenelol-a-nnphlhylmnine Do. I Beqd sh black ni-nitro-p-toluidine 2-(immninophenyl)-6-am1n0benzothlazol Ijl w red, p-chloro-o-loluhline Do. 1; by rat red p-p'-dinmino-diphenylam?Lie Do. shblack o-phenetol-a-nopluhylamine Do violet black One molecular proportion of the dinzoeompound of: Combined with the g 'g gg Shades nmmw-o-nnisidine 2-methyLG-nminobenzothiazol Bl'gish red p-ehloro-o-toluidine l Do. Btllllid'lt red e n a n I chum 111 which formula the phenyl residue 1n a-ddi- L0 1. As new compounds the azodyestufl's hevtion to the unnno group may be further subin; probably the general formula: stituted and R menus alkyl or the residue:

aryl v HO l phenylNIl-CO q 3. The process of producing new az0dyefl studs on the vegetable libre which comprises impregna ing the libre with a derivative oi 136 2.3-hydroxynaphthoic acid of the general formula I in which formula the phenylresidue in additlon to theamlno group may be further substituted, R means alkyl or the residue:

and developing then with any aromatic diazocompound not containing a sulfonlc grou 4;. illaterials dyed with the new azodyestuti's of claim 1, said dyestuffs being produced on the fibre of the material.

5. As new-compoumls the azodyestufis having probably the general formula:

ilaryl N t in which formula the phenyl residue in addition to the amino-group may be further subin which formula the phenyl residue in addition' to the amino-group may be further substitut-ed.

7. The process of producing new azo dyestuffs on the vegetable fibre which comprises impregnating the fiber with a derivative of 2.3-hydroxynaphthoic acid of the general formula:

in Which formula the phenyl residue in addition to the amino-group may be further substituted, and developing them with any aromatic diazocompound not containing a sulfonic group. I 8. Materials dyed with the new azodyestuffs of claim 5, said dyestuffs being produced on the fibre of the material.

In witness whereof I have hereunto signed my name this 7th day of October, 1927.

' V V WERNER ZERWECK. 

